THERMODYNAMICS, KINETICS, AND MECHANISMS OF SOLVATION, SOLVOLYSIS, AND SUBSTITUTION IN NON-AQUEOUS MEDIA

Rate constants (k), and the various transition state theory activation parameters (ΔGρ, ΔHρ TΔSρ, ΔVρ), reflect barriers between initial and transition states. Solvent effects on k and on AX* can be analysed into these two components if the reaction mechanism, kinetic data, and thermodynamic transfer parameters for the reactant(s) are all known. Examples of such analyses in organic and in inorganic chemistry, for substitution and for redox processes, are reviewed. Detailed consideration is given to a range of racemisation and isomerisation reactions, involving charged and uncharged, hydrophobic and hydroühilic substrates. Applications of such analyses to some organometallic reactions are given. This review concludes with a discussion of the use of volumes of activation in diagnosis of mechanism and of solvation in these and other systems. © 2013, Walter de Gruyter. All rights reserved.